Bio-additive for diesel fuel jet fuel, other fuels and lubricants

ABSTRACT

Compositions and methods of making bio-additives for diesel fuel, jet fuel and other fuels and lubricant formulations are presented. The compositions include a first polyalphaolefin, a second polyalphaolefin, a polyolefinic ester, a calcium overbased sulfonate, and a bean oil or seed oil. The fuel additives can be added to any fuel and result in advantages, such as a lower cloud point and a better lubricated engine.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation-in-Part of application Ser. No.13/726,584, filed Dec. 27, 2012 (Attorney Docket Number 89-4), entitled“BIO-ADDITIVE FOR DIESEL FUEL, JET FUEL, OTHER FUELS AND LUBRICANTS”which claims priority benefit of U.S. Provisional Patent Application No.61/580,589, filed Dec. 27, 2011 (Attorney Docket Number 89-2), entitled“BIO-ADDITIVE FOR DIESEL FUEL, JET FUEL, OTHER FUELS AND LUBRICANTS”, byClyde Ritter; this application is also a Continuation-in-Part ofapplication Ser. No. 13/937,951 (docket #89-5), entitled, “FUEL ADDITIVEAND METHOD FOR USE,” filed Jul. 9, 2013, by Clyde Ritter, which in turnclaims priority benefit of U.S. Provisional Patent Application No.61/669,345 (Docket #89-3), entitled “FUEL ADDITIVE AND METHOD FOR USE,”filed Jul. 9, 2012, by Clyde Ritter. The entire contents of all of theabove applications are incorporated herein by reference.

FIELD

This specification relates generally to biodiesel formulations andmethods of use.

BACKGROUND

The subject matter discussed in the background section should not beassumed to be prior art merely as a result of its mention in thebackground section. Similarly, a problem mentioned in the backgroundsection or associated with the subject matter of the background sectionshould not be assumed to have been previously recognized in the priorart. The subject matter in the background section merely representsdifferent approaches, which in and of themselves may also be inventions.

Biodiesel has been designated an alternative fuel by the U.S. Departmentof Energy and the U.S. Department of Transportation, and is registeredwith the U.S. Environmental Protection Agency as a fuel and fueladditive. Biodiesel can be used in any diesel engine (when blended withconventional diesel) and is compatible with existing petroleumdistribution infrastructure.

Specifications for biodiesel have been implemented in various countriesaround the world. In the U.S., the specifications have been implementedthrough the American Society of Testing and Materials (ASTM). The ASTMspecification for diesel is ASTM D975 and the ASTM standard forbiodiesel is ASTM D6751. It is noted that the standard for biodiesel isas a blendstock for blending into conventional diesel and is not meantto be a specification for B100 alone. It is noted that both No. 1 andNo. 2 petroleum diesel fuel (i.e., D1 and D2) can be blended withbiodiesel for various reasons, including the need for lower temperatureoperation.

Previously produced biodiesel fuels have a number of problems that makethem less desirable for use in fuels, including short shelf life, toomuch sulfur, the requirement for costly bonding agents, and a high cloudpoint.

SUMMARY

Methods of making bio-additives for diesel fuel, jet fuel and otherfuels and lubricant formulations are presented which include a firstpolyalphaolefin, a second polyalphaolefin, a polyolefinic ester, acalcium overbased sulfonate, and a bean oil or seed oil. The fueladditives can be added to any fuel and result in advantages such as alower cloud point.

Any of the above embodiments may be used alone or together with oneanother in any combination. The one or more implementations encompassedwithin this specification may also include embodiments that are onlypartially mentioned or alluded to or are not mentioned or alluded to atall in this brief summary or in the abstract. Although variousembodiments may have been motivated by various deficiencies with theprior art, which may be discussed or alluded to in one or more places inthe specification, the embodiments do not necessarily address any ofthese deficiencies. In other words, different embodiments may addressdifferent deficiencies that may be discussed in the specification. Someembodiments may only partially address some deficiencies or just onedeficiency that may be discussed in the specification, and someembodiments may not address any of these deficiencies.

BRIEF DESCRIPTION OF THE FIGURES

In the following drawings like reference numbers are used to refer tolike elements. Although the following figures depict various examples ofthe invention, the invention is not limited to the examples depicted inthe figures.

FIG. 1 shows a flowchart of an embodiment of a method of making abiodiesel fuel additive.

FIG. 2 shows a flowchart of an embodiment of a method of using thebiodiesel fuel additive in FIG. 1.

FIG. 3 shows a diagram of an embodiment of a system for making abiodiesel fuel additive.

DETAILED DESCRIPTION

Although various embodiments of the invention may have been motivated byvarious deficiencies with the prior art, which may be discussed oralluded to in one or more places in the specification, the embodimentsof the invention do not necessarily address any of these deficiencies.In other words, different embodiments of the invention may addressdifferent deficiencies that may be discussed in the specification. Someembodiments may only partially address some deficiencies or just onedeficiency that may be discussed in the specification, and someembodiments may not address any of these deficiencies.

Biodiesel is the name given to a variety of ester-based oxygenated fuelsmade from vegetable oils, fats, greases and other sources oftriglycerides. Biodiesel is a clean-burning diesel replacement fuel thatcan be used in compression ignition (CI) engines and is manufacturedfrom renewable non-petroleum-based sources, including: organic fats andoils (such as virgin vegetable oil), recycled oil (such as used fryeroil and grease trap materials), camelina sativa oil (false flax or wildflax oil), and animal fats (such as lard and beef tallow), for example.Non-limiting examples of these feedstocks include soybean oil, peanutoil, coconut oil, palm oil, canola oil (which can also be referred to asrapeseed oil), algae oil, jatropha oil, animal fat tallow, wastevegetable grease, and other similar sources.

The basic biodiesel reaction involves a transesterification process toconvert triglycerides in the feed stock to methylesters. Thetransesterification process typically involves the reaction of a raw oil(source of triglycerides) with methanol or ethanol and an alkalinecatalyst, such as sodium hydroxide or potassium hydroxide. Excessmethanol is typically used to ensure that the process is driven tocompletion.

The alcohol and catalyst are mixed first and then the alcohol/catalystmixture is mixed with the raw oil and allowed to react. Once thereactants are thoroughly mixed, the reaction begins and the raw oilbegins to separate into methylester and glycerin (otherwise known asglycerol). Because the methylester is less dense than the glycerin,methylester floats to the top of the glycerin and can be separated fromthe glycerin by pumping the methylester off the top or by draining theglycerin off the bottom. A centrifuge or other separation means can alsobe used to separate the methylester from the glycerin by-product.Thereafter, the methylester is purified to produce the biodieselproduct.

In this specification, biofuels are designated by the letter “B”followed by one to three digits, where the “B” indicates that the fuelincludes a biodiesel, and the one to three digits that follow indicatewhat percentage of the fuel that is biofuel. Thus, B23 represents a fuelthat 23 percent biofuel. Biodiesel is produced in pure form (100%biodiesel or “B100”), but is typically blended with conventional dieselat low levels between about 2% (B2) and about 20% (B20) in the U.S. andcan be blended at higher levels in other parts of the world. While B2biodiesels fuels can be used in conventional diesel engines withoutmodification, higher level blends above approximately B5 (and up toB100) can require special handling and fuel management as well asvehicle modifications, such as the use of heaters (especially in colderclimates) and different seals/gaskets that come into contact with thefuel. The level of care needed depends on a variety of factors,including: the engine, manufacturer, and climate conditions, amongothers.

FIG. 1 shows a flow chart of an embodiment of a method of making abiodiesel fuel additive B100 in which a fuel additive is produced havingthe properties provided herein.

Formulations of biodiesel fuel additives 100 can include a firstpolyalphaolefin, a second polyalphaolefin, a polyolefinic ester, acalcium overbased sulfonate, and a bean oil or seed oil. In otherformulations the biodiesel fuel additive does not have all of theelements or features listed and/or has other elements or featuresinstead of or in addition to those listed.

In step 102 one or more first polyalphaolefins are added and in step 104one or more second polyalphaolefins are added. In at least oneembodiment, the first polyalphaolefin centistoke number (kinematicviscosity) is different from the second polyalphaolefin centistokenumber. Polyalphaolefins are polymers produced from a simple olefin(also called an alkene with the general formula C_(n)H_(2n). Thepolyalphaolefin can be any polyalphaolefin having a centistoke value offrom about 2 to about 13. In some formulations, the firstpolyalphaolefin can be chosen from the group including: 2 centistoke, 3centistoke, 4 centistoke, 5 centistoke, 6 centistoke, 7 centistoke, 8centistoke, 9 centistoke, 10 centistoke, 11 centistoke, 12 centistoke,or 13 centistoke. In some formulations, the second polyalphaolefin canalso be chosen from the group including 2 centistoke, 3 centistoke, 4centistoke, 5 centistoke, 6 centistoke, 7 centistoke, 8 centistoke, 9centistoke, 10 centistoke, 11 centistoke, 12 centistoke or 13centistoke. In some formulations, the first and second polyalphaolefinare chosen to have different centistoke values. In some formulations,the first polyalphaolefin has a 6 centistoke value and the secondpolyalphaolefin has a 2 centistoke value. The first polyalphaolefin canbe included in the formulation for the biodiesel fuel additive at apercentage by volume of from about 4.5% to about 99.5%, including: 5,5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13,13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20,20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27,27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34,34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41,41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48,48.5, 49, 49.5, 50, 50.5, 51, 51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55,55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 60, 60.5, 61, 61.5, 70,71.5, 72, 72.5, 73, 73.5, 74, 74.5, 75, 75.5, 76, 76.5, 77, 77.5, 78,78.5, 79, 79.5, 80, 80.5, 81, 81.5, 82, 82.5, 83, 83.5, 84, 84.5, 85,85.5, 86, 86.5, 87, 87.5, 88, 88.5, 89, 89.5, 90, 91.5, 92, 92.5, 93,93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98.5, and 99%, forexample. In some formulations, the first polyalphaolefin is included inthe formulation for the biodiesel fuel additive at a percentage byvolume of from about 20 to 80%. In some formulations, the firstpolyalphaolefin is included at a percentage of from about 30 to 50%. Insome formulations, the first polyalphaolefin is included at a percentageof about 40%. In some formulations, the first polyalphaolefin isincluded at a percentage of from about 20% to about 80%. In someformulations, the first polyalphaolefin is included at a percentage offrom about 40% to about 60%. In some formulations, the amount ofpolyalphaolefin used depends on the desired outcome. For example,emission reduction versus improved fuel economy.

In step 104, a second polyalphaolefin can be included in theformulation. The second polyalphaolefin can be included in theformulation for the biodiesel fuel additive at a percentage by volume offrom about 95.5 to about 4.5%, including: 5, 5.5, 6, 6.5, 7, 7.5, 8,8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5,16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5,23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5,30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5,37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5,44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50, 50.5,51, 51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5,58, 58.5, 59, 59.5, 60, 60.5, 61, 61.5, 70, 71.5, 72, 72.5, 73, 73.5,74, 74.5, 75, 75.5, 76, 76.5, 77, 77.5, 78, 78.5, 79, 79.5, 80, 80.5,81, 81.5, 82, 82.5, 83, 83.5, 84, 84.5, 85, 85.5, 86, 86.5, 87, 87.5,88, 88.5, 89, 89.5, 90, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5,96, 96.5, 97, 97.5, 98, 98.5, and 99%, for example. In someformulations, the second polyalphaolefin is included in the formulationfor the biodiesel fuel additive at a percentage by volume of from about5 to 80%. In some formulations, the second polyalphaolefin is includedat a percentage of from about 5 to 30%. In some formulations, the secondpolyalphaolefin is included at a percentage of about 10%. In someformulations, the second polyalphaolefin is included at a percentage ofabout 30%. In some formulations, the second polyalphaolefin is includedat a percentage of from about 20% to about 80%. In some formulations,the second polyalphaolefin is included at a percentage of from about 40%to about 60%.

In step 106, at least one polyolefinic ester is included in theformulation of the fuel additive. Polyolefinic esters are a type of jetengine lube oil (for example HATCO product #3212, 3214, 1625 and mil-PRFtype C/I). The polyolefinic ester can be included at a percentage byvolume of about 4.5 to about 5.5%, including 4.6, 4.7, 4.8, 4.9, 5, 5.1,5.2, 5.3, 5.4, and 5.5%. In some formulations of the biodiesel fueladditive, the polyolefinic ester is included at 5%.

In step 108, at least one overbased detergent is included in theformulation of the fuel additive. One common overbased detergent iscalcium overbased sulfonate, although other overbased detergents alsowork. In this specification, an overbased detergent refers to adetergent, which typically a polar hydrophilic head with a hydrocarbontail, that has been overbased. Overbasing involves incorporatingadditional base reserve into an originally neutral detergent struction,usually in the form of a colloidally dispersed metal carbonate such asCaCO₃. Overbased detergents impart basicity to the oil to neutralizeacids formed during the combustion process and from degradiation of thelubricant. In addition, overbasing detergents impart other performanceenhancements, such as decreasing the dynamic coefficient of friction andacting as rust and corrosion inhibitors. Preferably, the excess metal ispresent over that which is required to neutralize the acids. In thisspecification, the term “overbased sulfonate” includes any metallic saltof sulfonic acid compound(s) having “a metal content in excess of thatwhich would be present according to the stoichiometry of the metal andthe acidic organic compound reacted with the metal” including compoundsdesignated as “superbased sulfonates”, “overbased petroleum sulfonates”,“overbased alkaline-earth sulfonates”, and “natural-based”, “syntheticbased”, or “natural-synthetic blend” overbased sulfonates, for example.Calcium overbased sulfonates are detergents that can be diesel additivesand are designed to clean metal surfaces within an engine and preventthe build-up of deposits. The C400-C™ Overbased Sulfonate ismanufactured by Surpass Chemicals Limited, 10 Chemical court, West Hill,Ontario Canada, M1E3X7 and marketed by Witco Corporation, One AmericanLane, Greenwich Conn., USA 06831-2559. The calcium overbased sulfonatecan be used at a particle size of from about 50 to about 100 angstroms,including 55, 60, 65, 70, 75, 80, 85, 90, and 95 angstroms or mixturesthereof. The calcium overbased sulfonate can be included in theformulation for the biodiesel fuel additive at a percentage by volume ofabout 4.5 to about 80.5%, including: 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9,9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16,16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23,23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30,30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37,37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44,44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50, 50.5, 51,51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58,58.5, 59, 59.5, 60, 60.5, 61, 61.5, 70, 71.5, 72, 72.5, 73, 73.5, 74,74.5, 75, 75.5, 76, 76.5, 77, 77.5, 78, 78.5, 79, 79.5, and 80%. In someformulations, the calcium overbased sulfonate is included at a volume offrom about 5 to about 25%. In some formulations, the calcium overbasedsulfonate is included at a volume of 5%. In some formulations, thecalcium overbased sulfonate is included at a volume of 25%. In someformulations, the calcium overbased sulfonate is included at a volume of40%. In some formulations, the calcium overbased sulfonate (C-400) isused at a percentage that reduces visible smoke from the diesel or otherequipment.

In step 110, at least one bean oil or seed oil is included in theformulation of the fuel additive. At least one bean oil or seed oil canbe included, such as castor oil, soybean oil, peanut oil, coconut oil,palm oil, canola oil, rapeseed oil, camelina sativa oil, jatropha oil,or combinations thereof. The bean oil or seed oil can be included at apercentage by volume of about 19.5% to about 20.5%, including 19.6%,19.7%, 19.8%, 19.9%, 20%, 20.1%, 20.2%, 20.3%, 20.4%, and 20.5%, forexample. In some formulations, the bean oil or seed oil is included at20%. In some formulations, the bean oil or seed oil is castor oil. Insome formulations, the castor oil is used at a concentration thatreduces measured emissions.

In step 112, the ingredients or formulation is mixed. In step 112 themixture is mixed at a temperature of between about 70° F. to about 80°F. until the components are completely mixed (e.g., the composition ishomogeneous). In an embodiment, the method of mixing can include anyappropriate method including mechanical stirring at a low to mediumspeed. In at least one embodiment, the mixing is by continuous mildmechanical agitation. The method of mixing may use any type of mixer oragitator. In at least one embodiment, standard rotational mixingequipment (e.g., a paint mixer) is used. In some embodiments, the firstpolyalphaolefin, a second polyalphaolefin, a polyolefinic ester, acalcium overbased sulfonate, and bean oil or seed oil are admixed at atemperature of from about 72° F. to 78° F., including 73° F., 74° F.,75° F., 76° F., and 77° F. In some embodiments the firstpolyalphaolefin, a second polyalphaolefin, a polyolefinic ester, acalcium overbased sulfonate, and bean oil or seed oil are admixed atabout 76° F.

In some embodiments, the method involves premixing the polyalphaolefins(PAO) and then adding the polyolefinic ester (POE) making a PAO/POEblend (PAO/POE), admixing 10% of the PAO/POE blend with the calciumoverbased sulfonate, slowly adding the bean oil or seed oil to the mix,mixing thoroughly, and adding the remaining PAO/POE blend. In someembodiments, adding the PAO/POE blend improves emissions, makes thebiodiesel fuel additive relatively impervious to temperature extremes(having a wider temperature range in the fuel is usable than were thebiodiesel fuel not added), and lowers the cloud point character.

In some embodiments, the biodiesel fuel additive is stored at atemperature of about 70-74° F., including 71° F., 72° F., and 73° F. Insome embodiments, the biodiesel fuel additive is stored at a temperatureof about 72° F. In some embodiments, the biodiesel fuel additive isstored at room temperature (e.g., 68° F. to 77° F.).

In another embodiment, although depicted as distinct steps in FIG. 1,steps 102-112 may not be distinct steps. In other embodiments, method100 may not have all of the above steps and/or may have other steps inaddition to or instead of those listed above. The steps of method 100may be performed in another order. Subsets of the steps listed above aspart of method 100 may be used to form their own method.

The method of preparing a biodiesel fuel additive B100, comprisesadmixing a first polyalphaolefin, a second polyalphaolefin, apolyolefinic ester, a calcium overbased sulfonate, and a bean oil orseed oil. In other formulations, the biodiesel fuel additive does nothave all of the elements or features listed and/or has other elements orfeatures instead of or in addition to those listed. In some embodiments,the bean oil or seed oil is castor oil.

FIG. 2 shows a flow chart of an embodiment of a method of using a fueladditive 200 in which a fuel additive is used alone or admixed with afuel.

In step 210, the type of engine is identified in which the fuel additivewill be used. The engine might be a diesel engine, an automobile engine(a gas engine) or a jet engine. The type of engine can influence thecomposition of the fuel additive. Thus, for example, a jet fuel mighthave a lower percentage of degummed lipid acid or ester and/or castorbean oil (see, for example, Example 3). A decision can be made at thispoint whether to use the fuel additive alone as the fuel or to use afuel composition of the fuel additive mixed with a fuel.

The fuel additive can be mixed with a fuel to create a fuel composition.In step 220, the fuel additive is mixed with a fuel. In some embodimentsthe fuel additive is admixed with before-market or after-market fuels.In some embodiments, the fuel additive is admixed with conventionaldiesel, biofuels, avgas, automobile gas, jetfuel and/or engine oil atabout 2 to about 99%, including 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32,33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50,51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68,69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86,87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99%, for example. Insome embodiments, the fuel additive is admixed with regulated orunregulated diesel at about 2 to about 20%. In some embodiments, thefuel additive is admixed with biodiesel at about 2 to about 20%. In someembodiments, the fuel additive is admixed with avgas at 1 oz. per 10gallons, including: 1 oz. per 5 gallons, 6 gallons, 7 gallons, 8gallons, 9 gallons, 10 gallons, 11 gallons, 12 gallons 13 gallons, 14gallons and 15 gallons. In some embodiments, the fuel additive isadmixed with automobile gas and/or jet fuel at 1 oz. per 15 gallonsfuel, including: 1 oz. per 5 gallons, 6 gallons, 7 gallons, 8 gallons, 9gallons, 10 gallons, 11 gallons, 12 gallons 13 gallons, 14 gallons, 15gallons, 16 gallons, 17 gallons, 18 gallons, 19 gallons, and 20 gallons.

In some embodiments, the biodiesel fuel additive is admixed withconventional diesel at about 2 to about 20%. In some embodiments, thebiodiesel fuel additive is admixed with avgas at 1 oz. per 10 gallons.In some embodiments, the biodiesel fuel additive is admixed withaircraft engine oil at 1 oz. per 2 quarts (qts). In some embodiments,the biodiesel fuel additive is admixed with automobile gas and/or jetfuel at 1 oz. per 15 gallons fuel.

In step 230, the fuel additive is used alone as a fuel. The fueladditive can be used in any appropriate engine. The fuel additive can bedirectly added to the fuel tank in the engine.

In step 250, the fuel additive is added to an engine. The fuel additivecan be added to any type of engine discussed herein.

In another embodiment, although depicted as distinct steps in FIG. 2,steps 210-250 may not be distinct steps. In other embodiments, method200 may not have all of the above steps and/or may have other steps inaddition to or instead of those listed above. The steps of method 200may be performed in another order. Subsets of the steps listed above aspart of method 200 may be used to form their own method.

In some embodiments, each of the steps of the method is a distinct step.In another embodiment, although depicted as distinct steps in the abovedescription, may not be distinct steps. In other embodiments, the abovemethod may not have all of the above steps and/or may have other stepsin addition to or instead of those listed above. The steps of the abovemethod may be performed in another order. Subsets of the steps listedabove as part of method may be used to form their own method.

FIG. 3 illustrates a block diagram of an embodiment of a system formaking a bio-fuel additive 300 in which a bio-additive is producedhaving the properties provided herein. System 300 can include containerfor a first centistoke polyalphaolefin 310; a container for a secondcentistoke polyalphaolefin 320; container for polyolefinic ester 330;container for calcium overbased sulfonate 340; container for bean oil orseed oil 345; controller 350, pumps 355 a-d, vat 390, and stirringapparatus 395. In other embodiments, environment 300 can not have all ofthe components listed and/or can have other elements instead of, or inaddition to, those listed above.

Reference to biofuel additives 300 and biodiesel fuel additives is notintended to limit the additive to a particular fuel or to an additive.The biodiesel fuel additive can be used in any fuels discussed hereinand/or that would be enhanced by the fuel additive. The word biofueladditive, biodiesel fuel additive, biodiesel additive, fuel additive,and biodiesel formulations may interchangeably with one another anywherein the specification to obtain different embodiments. Further, thebiodiesel fuel additive may be used alone as a fuel.

Examples of formulations of a biodiesel fuel additive 300 are providedthat can be used blended with another fuel or oil. In some formulationsthe biodiesel fuel additive is blended with conventional biodiesel fuel(or oil) at concentrations of from about 1% to about 99% by volume(e.g., from 1% to 99%). Some formulations of the biodiesel fuel additivecan be blended with conventional biodiesel fuel at 2% (B2) to 20% (B20)for use in conventional biodiesel engines throughout the world. Higherlevel blends (5% —B5 and higher) can be used in conventional dieselengines with some modifications, including: adding a heater to keep thebiofuel above a certain temperature, different seals/gaskets may beneeded to prevent the blend with the biodiesel from leaking, separationfrom petroleum fuels at low temperatures, special handling, and fuelmanagement.

While the biodiesel fuel additive 300 has utility as a biodiesel fueland/or additive, it can also be used as a fuel additive in other typesof fuels or oils without limitation, including: jet fuel, avgas(aviation gasoline), kerosene, lubrication oil, and fuel for any2-stroke engine. In addition, the biodiesel fuel additive can also beused in engine oils without limitation.

The system for making a fuel additive 300 can be an industrial processthat includes a system for preparing the ingredients (the firstpolyalphaolefin; the second polyalphaolefin; the polyolefinic ester; thecalcium overbased sulfonate; and the bean oil or seed oil). Theindustrial process can also include a system for storing the ingredientsin a tank and adding the amount of each ingredient depending on thespecific fuel additive being produced (e.g., a fuel additive for anavgas). The amount of each ingredient can be measured using a computerto program the addition. The industrial process can also includestirring the ingredients to make a homogeneous mixture. The system mayalso include a facilities for mixing the fuel additive with a fuel.

The container for first polyalphaolefin 310 provides a holding place forthe ingredient before it is mixed with the other ingredients that makeup the fuel additive. The container 310 can be a tank or any suitableholding container. The types of polyalphaolefins that can be used arediscussed with reference to FIG. 1. The container 310 can be any type ofcontainer as long as container 310 does not change the chemistry of thefirst polyalphaolefin. In other words, the container may be composed ofan inert material. Alternatively, the container can be coated with aninert material. The container can include one or more pipes or flexibletubes that allow for movement of the first polyalphaolefins into acentral mixing bowl or vat. The movement of the materials as well as howmuch of the material is added, may be controlled with one or more pumpsthat may be activated by a central computer.

The container for second polyalphaolefin 320 includes a holding placefor one or more second polyalphaolefins before the ingredient is mixedwith the other ingredients to make up the fuel additive. The containerfor the second polyalphaolefin 320 can be configured to work like thecontainer for the first polyalphaolefin 310.

The container for polyolefinic ester 330 and the container for calciumoverbased sulfonate 340 can be produced and attached to the vat ormixing container substantially as described for the container for thefirst and second polyalphaolefins 310.

The container for the bean oil or seed oil 345 can be produced andattached to the vat or mixing container substantially as described forthe container for the first and second polyalphaolefins 310. However,because the content of the container is an oil, the container may notneed to be coated with a specialized material. Since the order ofaddition of the ingredients to produce the fuel additive is notimportant, the ingredients can be directly added to the vat and/or thepipes can be configured as a single pipe with each ingredient added to acentral pipe on the way to the vat. Alternatively, each ingredient mayenter the vat via a separate pipe.

The controller 350 functions to monitor and control the process ofmixing the ingredients in the specified ratio. The controller 350 canfunction to control the pumps and control the amount of each ingredientthat is added to the vat. The pumps that are attached to the pipes ortubes for each of the ingredients can be controlled by the controller.The ingredients, including the first polyalphaolefin, the secondpolyalphaolefin, the polyolefinic ester, the calcium overbasedsulfonate, and the bean or seed oil can be added in the specificpercentages discussed in FIG. 1 for each type of fuel additive. Thecontroller 350 can control the amount of each ingredient to be allowedinto the pipes and finally poured into the vat to produce the fueladditive. The controller 350 can be programmed to allow differentpercentages of each ingredient into the central vat. Thus, for example,the controller can be programmed to produce the fuel additive in Example1 to have 40% 6 centistoke polyalphaolefin, 30% 2 centistokepolyalphaolefin, 5% polyolefinic ester, 5% calcium overbased sulfonate,and 20% castor oil. In at least one embodiment, the controller 350 canalso sense whether the containers for each ingredient (310, 320, 330,340 and 345) have less than the amount of the ingredient for a vat ofthe fuel additive. Although there may be a range of percentages of eachingredient that works well for different uses, the system may ensurethat there is a good quality control, so that the customer gets the samefuel additive each time.

In at least one embodiment, the controller 350 includes a sensorfeedback mechanism for each ingredient. A sensor detects the amount ofthe particular ingredient leaving the pipe into the vat and/or thepercentage of that ingredient in the vat. Then, controller 350 adjustthe flow of the ingredient to ensure that the intended amount of theingredient is added to the vat and/or the mixture in the vat has theintended percentage of that ingredient. Controlling the flow of theingredient may include increasing and/or decreasing the flow of theingredient in the vat. Controlling the flow of the ingredient may alsoturning the pump and opening an valve to start adding the desiredingredient or shutting the valve and turning off the pump to stop addingthe ingredient. In at least one embodiment, the controller 350 includesa sensor feedback mechanism for each ingredient for determining whetherthe tank storing the ingredient is empty and/or low.

The pumps 355 a-d work with the controller 350 to precisely add theamount of each ingredient to the vat. The pumps can be any type of pump.In at least one embodiment, the pumps 355 a-d are activated by thecontroller 350.

The vat 390 can be any type of container that allows for the mixing ofthe ingredients to make up the fuel additive. For example, the vat 390can be an industrial size mixing bowl. The vat 390 can include atemperature control and/or refrigeration or heating device as needed.The vat 390 can include a stirring apparatus to allow for completemixing of the ingredients. The stirring apparatus can be any type ofindustrial mixer or agitator. In at least one embodiment, standardrotational mixing equipment (a paint mixer) is used. The vat 390 can beof a size that allows for mixing a large amount of fuel additive for usealone or as a fuel additive.

The stirring apparatus 395 can be contained within the vat 390 or can beadded to the vat 390 to mix the ingredients completely, but at a slow tomoderate speed. The stirring apparatus can be controlled by thecontroller 350 or by separate means. In at least one embodiment, a timercan be added to the stirring apparatus to control the amount of timethat the ingredients are mixed to a homogeneous mixture. In at least oneembodiment, a speed control can be added to the stirring apparatus tocontrol and/or change the speed of mixing.

In an embodiment the fuel additive can be stored alone at roomtemperature (e.g., approximately 72° F.) for up to 6 months. In anotherembodiment, the fuel may be stored for up to 7, 8, 9, 10, 11, or 12months. The biodiesel fuel additive can be stored mixed with fuel atroom temperature for up to 6 months including 7, 8, 9, 10, 11, and 12months. The fuel additive can be stored for at least 6 months at −10° F.and +90° F., with no visible affects.

Synthetic biodiesel fuel additives are provided in Examples 1 and 2.

Example 1

Provided in example 1 is a biodiesel fuel additive for emissionsreduction and lowering the cloud point of diesel, biodiesel and jetfuel. The biodiesel fuel additive can be blended with bio fuels toinclude 100% biodiesel, where the percentage represents the percentageof biodiesel by volume. The biodiesel fuel additive is a syntheticproduct because the biodiesel fuel additive is chemically refined fromcomponents other than crude oil. The cloud point is significant in theU.S. because biodiesels produced from different feedstocks can performdifferently in different geographic regions and climates. The cloudpoint test is performed as part of ASTM 6751 testing to characterize thelow temperature operability of diesel fuel. The cloud point test definesthe temperature at which a cloud or haze appears in the fuel underprescribed test conditions. The cloud point for biodiesel blends isgenerally higher than the cloud point is for petroleum diesel fuel. Thecloud point for the formula in example 1 was −33° F. The biodiesel fueladditive included:

40%—6 centistoke polyalphaolefin

30%—2 centistoke polyalphaolefin

5%—polyolefinic ester

5%—calcium overbased sulfonate

20%—castor oil

_(———)

100% total composite mix.

The mixture was mixed at 76° F. The mixture was stored at roomtemperature (72° F.). The blending procedure involved pre-mixing the 2and 6 centistoke polyalphaolefin (PAO), then adding the 5% polyolefinicester (POE). Then the calcium overbased sulfonate was mixed with 10% (byvolume) of the PAO/POE blend using standard rotational mixing equipment(a paint mixer). The castor oil was added slowly to the mix and, afterthoroughly blending (10 minutes), the remaining PAO/POE blend was added.Without being limited to the following analysis, the polyolefinic esterappears to be the catalyst. No purification was needed and there was nospecial storage requirement. The formulation involved a meteredapplication of the components.

This formulation specifically lowered the cloud point and reduced thevisible smoke from diesel, biodiesel and jet fuel combinations.

Example 2

Provided in example 2 is a second formulation of a biodiesel fueladditive to lower emissions and improve fuel economy of diesel and jetengines using any applicable fuels, straight or bio blends (The % ispercentage by volume). The cloud point for the formula shown in Example2 was −25° F. The biodiesel fuel additive included:

40%—6 centistoke polyalphaolefin

10%—2 centistoke polyalphaolefin

20%—castor oil

5%—polyolefinic ester

25%—calcium overbased sulfonate

_(———)

100% total composite mix.

The mixture was mixed at 76° F. The mixture was stored at roomtemperature (72° F.). The blending procedure involved pre-mixing the 2and 6 centistoke polyalphaolefin (PAO), then adding the 5% polyolefinicester (POE). Then the calcium overbased sulfonate was mixed with 10% (byvolume) of the PAO/POE blend using standard rotational mixing equipment(a paint mixer). The castor oil was added slowly to the mix and afterthoroughly blending (10 minutes), the remaining PAO/POE blend was added.Without being limited to the following analysis, the polyolefinic esterappears to be the catalyst. No purification was needed and there was nospecial storage requirement. The formulation involved a meteredapplication of the components.

The formulation in example 2 was thicker and more expensive than thatshown in example 1, but the formulation in example 2 exhibited all ofthe benefits of the formulation in example 1 as well as improved fueleconomy.

Polyalphaolefins are available in several different viscosities statedin centistokes (cts) i.e.; (2 through 13 cts.) All viscocities can beused in the formulation to optimize the formula for differentapplications. Calcium overbased sulfonates are also varied, though,using the Chemtura product nomenclature, C-400CR is preferred for abiodiesel fuel additive to lower emissions and improve fuel economy ofdiesel and jet engines.

The formulas shown in Examples 1 and 2 were tested in certified labs andit was found that the formulations in examples 1 and 2 did not take anyof the fuels tested out of spec, either ASTM or Mil spec. ASTM dieselfuel testing was performed under D-975 06-B, ASTM tests for gasolinewere performed under D-4814, and jet fuels were tested under ASTM D-156,D-4176, D-86, D-1298, D-2386, D-130, D-381, D-1094, D-3948, D-93,D-3241, D-6304, and D-2276.

Both formulations in Examples 1 and 2 withstood storage for 6 months at−10° F. and +90° F., with no visible affects.

Example 3 provides a comparison of the properties of the biodiesel fueladditives as compared to a comparable fuel provided in U.S. Pat. No.5,505,867.

Example 3

The biodiesel fuel additives shown in Examples 2 and 3 were compared toa comparable fuel additive provided in U.S. Pat. No. 5,505,867. The fuelin U.S. Pat. No. 5,505,867 consisted of 40% overbased sulfonate/10%jojoba oil/50% castor oil blended as taught therein. A variety ofproperties were tested including shelf life, freezing temperature,behavior at low temperatures, sulfur content, cloud point of fuels whenmixed at a variety of concentrations, and lubrication ability. The testswere performed as follows:

Lubrication measures the anti-weld properties at point of contact.Lubrication was measured using the four ball test. In summary, threeballs were put in a cylinder and the fourth ball was put on top and wasspring loaded (to apply pressure to the other three balls). Thebiodiesel fuel additive (alone or mixed with fuel) was added, and thebottom of the cylinder was spun to make the balls wear. The number ofmillimeters of depth of the scar caused by the wearing was measured.Using the biodiesel fuel additives in examples 1 and 2, surprisingly theballs actually wore to a mirror finish, probably as a result of thecalcium bonding to the balls. Thus, the calcium can prevent the parts inan engine from sticking.

The emissions test involved using a reference card. The reference cardwas a card with circles with balls inside. A wafer was placed in thetail pipe forcing the exhaust through the wafer, which had theappearance of the ball with the circle around it. On the reference card,the ball and circle #0 represented no engine running and the one withthe highest number #9 was the engine running with nothing to filter theoutput. Two measurements were taken 20 minutes apart. The firstmeasurement immediately after adding the biodiesel additive was higherthan #9.After 20 minutes running with the biodiesel additive, themeasurement was reduced to between 2 and 3, showing a significantreduction in emissions. The specific emissions measurements are shown inTables 1 and 2:

TABLE 1 Properties of Biofuel of USPN 5,505,867 Positive NegativePerforms as advertised Shelf life very short - separates in hours Simpleto formulate Freezes solid at near 0° F. Keeps biodiesel in suspensionToo much sulfur, cannot be sold in in diesel fuels at low temps.regulated fuels Reduces friction and wear on Cannot be used in jetfuels.(triglycerides) all interfacing parts of engine and fuel deliverysystems. Reduces emissions. Patent states any calcium in suspensionRequires costly bonding agent in formula. Does not lower cloud point ofany fuels

TABLE 2 Properties of new synthetic-based product Positive NegativeIndefinite shelf life The formulation involves metered application ofcomponents Will not freeze Lowers cloud point of diesel, biodiesel, jetfuels and bio-jetfuels by 25° F. Keeps any biofuels added to diesel andjetfuels in suspension indefinitely in low temps. Preservative forrubber and elastomers in fuel systems. Provides superior lubrication forpoint of contact metals and all other components in fuel systems.Reduces measured emissions from diesel and jet engines. (measured 14% ofcarbon emissions.) Less costly to formulate than original product.Reduces triglycerides by 80% compared to original product. Does not takeany fuels out of specifications (ASTM or Mil Spec)

The soot reduction test measured the initial emissions reduction withthe new synthetic product (the biodiesel fuel additives in examples 1and 2) using the ECOM unit. The soot reduction test was performed on thebiodiesel fuel additive from Examples 1 and 2 as follows: a Yanmar 20 hp(horsepower) 3 cylinder diesel with a 21.6 compression ratio wasinstalled in a John Deere model 430 Tractor™. The engine had never beenexposed to Ca-40 g fuel additive and had 1900 hours total run time as acommercial operation equipment. The first smoke test was a test with noadditive applied. The results were in the form of a wafer supplied withthe ECOM portable testing unit. A copy of the soot comparison chart wasincluded for graphic comparison. With the additive applied and theengine run for 2 hours prior to testing, the following results wereobtained for the emissions and soot tests: the measured toxic emissionsrecorded a slight reduction in CO₂ by 12%, a reduction in NOX by 14%, anincrease in O₂ by 10%, and a reduction in measured soot by 80% ascompared to how the engine ran without the additive.

The reduction in measured soot was very significant. The engine noisewas considerably reduced. Odor was reduced to an almost imperceptiblelevel. After 3 hours run time with the biodiesel fuel additive inexamples 1 and 2, the engine picked up idle speed and had to be slowedback to 1200 rpm. Thus, engines using the additive in examples 1 and 2ran significantly more quietly and put out about 10% more oxygen.

The freeze test was performed for 10 months at the temperaturesdiscussed. The test at 90° F. was performed for 3 months. The freezetest can include the pour point and/or the cloud point. The pour pointis the lowest temperature at which the fuel or fuel with the productapplied is still liquid enough to allow a paddle in a small containersubmersed in ice and methanol (called the Brookfield test).

The freeze test can also reference the cloud point, which is thetemperature at which wax crystals form, clump together and clog fuelfilters (fuel filters typically have a 5μ porosity). The cloud point isa better measure of freezing point. Untreated diesel/jet fuels will pourat −40° F., but will cloud up at −8° F. The low temperature degradationof the biodiesel fuel additives in examples 1 and 2 were tested for 10months and no change was seen. It is likely that there would be nochange for much longer, even 10 years.

The actual testing of jet fuel with the fuel additive of example 1 wasat −33° F., but it is likely there will be no low temperaturedegradation up to −42° F. and even −47° F. Cloud point testing was donewith diesel/jet fuels having the additive of example 1 applied at 1 ozper 10 gallons fuel.

The pour point of the additives in examples 1 and 2 was tested at −30°F. by the Brookfield method alone (without added fuel). This is because,once added to fuels, the pour point is referencing fuel treated with theadditive.

Example 6

2-stroke engines include small, portable, or specialized machineapplications such as outboard motors, high-performance, small-capacitymotorcycles, mopeds, underbones, scooters, tuk-tuks, snowmobiles, karts,ultralights, model airplanes (and other model vehicles) and lawnmowers.The two-stroke cycle is used in many diesel engines, most notably largeindustrial and marine engines, as well as some trucks and heavymachinery.

The biodiesel fuel additive taught in example 2 was used in a typical 2stroke engine at ¼oz per gal of gasoline in a leaf blower with very goodresults. As a two stroke replacement the biofuel additive increased theefficiency and/or decreased the fuel consumption by 20%. In addition,when the biodiesel fuel additive was used, there was no smoke or odorfrom the exhaust of the engine. When jet skis were run with the example2 fuel additive (¼ oz per gallon of gasoline), there was no oil slick onthe water. Using the fuel additive from example 2 (¼ oz per gallon ofgasoline) did not build deposits in any of the engines tested.

Example 7

Aviation gasoline (Avgas) is a high-octane aviation fuel used to powermany aircraft and racing cars. In Avgas, the additive taught in examples1 and 2 can replace the tetraethyl lead because the formulations taughtin examples 1 and 2 perform the same function by controlling combustionas well as lubricity for the valve/seat operation.

The biodiesels taught in examples 1 and 2 were used in jet enginesand/or in engine oil following ASTM D-1655-82 Mil spec 85470. The treatrate refers to the amount of additive that is added to the fuel and isgiven as the amount of additive per the amount of fuel. The “treatedfuel”, “treated oil”, etc. means that the fuel or oil includes a dose ofthe additive. The treat rate for avgas was 1 oz. per 10 gals. Avgas and1 oz. per 2 quarts (qts) aircraft engine oil (the treat rate for autogas, diesel and jet fuel is 1 oz. per 15 gals. fuel). There were manyimprovements shown when using the biodiesels in examples 1 and 2,including 10% improvement in fuel economy. In use, the biodiesel fueladditives from examples 1 and 2 did not build deposits in the combustionchamber. Thus, the synthetic biodiesel of examples 1 and 2 can be usedas a replacement for tetraethyl lead in aviation gasoline and can beused to lower the Reid vapor pressure in avgas.

Each embodiment disclosed herein may be used or otherwise combined withany of the other embodiments disclosed. Any element of any embodimentmay be used in any embodiment.

Although the invention has been described with reference to specificembodiments, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the true spirit and scope of theinvention. In addition, modifications may be made without departing fromthe essential teachings of the invention.

1. A biodiesel composition comprising: from about 4.5% to about 95.5% ofa first 2-13 centistoke polyalphaolefin; from about 95.5% to about 4.5%of a second 2-13 centistoke polyalphaolefin; from about 4.5% to about5.5% polyolefinic ester; from about 4.5% to about 80.5% calciumoverbased sulfonate; and from about 19.5% to about 20.5% bean oil orseed oil, wherein the first and second polyalphaolefins have differentcentistokes values and wherein the particle size of the calcium isbetween about 50 and 100 angstroms.
 2. The biodiesel composition ofclaim 1, wherein the viscosity value of the first polyalphaolefin is 6centistoke.
 3. The biodiesel composition of claim 1, wherein theviscosity value of the second polyalphaolefin is 2 centistoke.
 4. Thebiodiesel composition of claim 1, wherein the calcium overbasedsulfonate is a C-400CR calcium overbased sulfonate.
 5. The biodieselcomposition of claim 1, wherein the bean oil or seed oil is castor oil.6. The biodiesel composition of claim 1, wherein the composition has ashelf life of at least 9 months.
 7. The biodiesel composition of claim1, wherein the composition will not freeze up to a temperature of −33°F.
 8. The biodiesel composition of claim 1, wherein the addition todiesel, biodiesel, jet fuel, or bio jet fuels lowers the cloud point byat least 10° F.
 9. The biodiesel composition of claim 7, wherein thecloud point is lowered by at least 25° F.
 10. The biodiesel compositionof claim 1, wherein the addition to diesel, biodiesel, jet fuel, or biojet fuels reduces carbon emissions by at least 10%.
 11. The biodieselcomposition of claim 9, wherein the addition to diesel, biodiesel, jetfuel, or bio jet fuels reduces carbon emissions by at least 14%.
 12. Amethod of making a biodiesel fuel additive composition comprising:combining at least from about 4.5% to about 95.5% of a first 2-13centistoke polyalphaolefin; with from about 95.5% to about 5.5% of asecond 2-13 centistoke polyalphaolefin; with from about 4.5% to about5.5% polyolefinic ester with; from about 4.5% to about 80.5% calciumoverbased sulfonate; and with from about 19.5% to about 20.5% bean oilor seed oil, wherein the first and second polyalphaolefins havedifferent centistoke values and wherein the particle size of the calciumis between about 50 and 100 angstroms.
 13. A method of using a biodieselfuel additive composition comprising: adding into a fuel tank of anengine composition including at least from about 4.5% to about 90.5% ofa first 2-13 centistoke polyalphaolefin; with from about 95.5% to about4.5% of a second 2-13 centistoke polyalphaolefin; with from about 4.5%to about 5.5% polyolefinic ester with; from about 4.5% to about 80.5%calcium overbased sulfonate; and with from about 19.5% to about 20.5%bean oil or seed oil, wherein the first and second polyalphaolefins havedifferent centistokes values and wherein the particle size of thecalcium is between about 50 and 100 angstroms; and running the engine oncontents in the fuel tank.
 14. The method of claim 13, wherein the beanoil or seed oil is castor oil.
 15. The method of claim 13, wherein thecomposition is admixed at a temperature of about 76° F.
 16. The methodof claim 13, wherein the composition is stored at a temperature of about72° F.
 17. The method of claim 13, further comprising mixing thebiodiesel fuel additive with conventional diesel at a concentration ofabout 2% to about 20%.
 18. The method of claim 14, wherein thecomposition is admixed at a temperature of about 76° F.
 19. The methodof claim 14, wherein the composition is stored at a temperature of about72° F.
 20. The method of claim 14, further comprising mixing thebiodiesel fuel additive with conventional diesel at a concentration ofabout 2% to about 20%.
 21. The method of claim 13, further comprisingpremixing the polyalphaolefins (PAO) and then adding the polyolefinicester (POE) making a PAO/POE blend (PAO/POE).
 22. The method of claim22, further comprising admixing 10% of the PAO/POE blend with thecalcium overbased sulfonate.
 23. The method of claim 23, furthercomprising slowly adding the bean oil or seed oil to the mix.
 24. Themethod of claim 24, further comprising mixing until homogeneous.
 25. Themethod of claim 25, further comprising adding the remaining PAO/POEblend.